Process for the preparation of halogenated hydroxydiphenyl compounds

Abstract

A process for the preparation of halohydroxydiphenyl compounds useful for protecting organic materials and articles from microorganisms, of the formula by acylation of a halogenated benzene compound (first stage), etherification of the acylated compound with a halogenated phenol compound (second stage), oxidation of the etherified compound (third stage) and hydrolysis of the oxidized compound in a fourth stage, according to the following reaction scheme: in which R 1 and R 2 independently of one another are F, Cl or Br; R 3 and R 4 independently of one another are hydrogen; or C 1 -C 4 alkyl; m is 1 to 3; and n is 1 or 2.

What is claimed is:  
     
       1. A process for the preparation of a chlorinated hydroxydiphenyl compound of the formula                    
       by acylation of a chlorinated benzene compound (first stage), etherification of the acylated compound with a chlorinated phenol compound in the presence of a strong organic or inorganic base, wherein the molar ratio of the base to the chlorinated phenol is from 0.5:1 to 0.3:1, a copper catalyst and an inert organic solvent selected from the group consisting of toluene, xylene and a xylene isomer mixture (second stage), oxidation of the etherified compound (third stage) and hydrolysis of the oxidized compound in a fourth stage, according to the following reaction scheme:                    
       wherein m is 1 or 2. 
     
     
       2. A process according to claim  1 , wherein in the acylation reaction (first stage) the compound of the formula (5′) is formed. 
     
     
       3. A process according to claim  1 , wherein the acylation reaction (first stage) is carried out in the presence of a Lewis acid. 
     
     
       4. A process according to claim  1 , wherein acetyl chloride is used for the acylation reaction. 
     
     
       5. A process according to claim  1 , wherein in the etherification (second stage) the compound of the formula (7′) is formed. 
     
     
       6. A process according to claim  1 , wherein in the oxidation (third stage) the compound of the formula (8′) is formed. 
     
     
       7. A process according to claim  1 , wherein the oxidation is carried out in the presence of m-chloroperbenzoic acid. 
     
     
       8. A process according to claim  1 , wherein the oxidation is carried out in the presence of a mixture of sodium borate and trifluoroacetic acid. 
     
     
       9. A process according to claim  1 , which relates to the preparation of compounds of the formula (9) in which 
       m is 2.  
     
     
       10. A process according to claim  1 , which relates to the preparation of compounds of the formula (9) in which 
       m is 1.  
     
     
       11. A process according to claim  1 , which relates to the preparation of the compound of the formula                    
     
     
       12. A process according to claim  1 , which relates to the preparation of the compound of the formula                    
     
     
       13. A process according to claim  1 , wherein the oxidation is carried out in the presence of a mixture of a mixture of acetic anhydride, sulfuric acid and H 2 O 2 .